EP2307495B1 - Compositions comprising thermoplastic starch - Google Patents

Compositions comprising thermoplastic starch Download PDF

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Publication number
EP2307495B1
EP2307495B1 EP09802282.5A EP09802282A EP2307495B1 EP 2307495 B1 EP2307495 B1 EP 2307495B1 EP 09802282 A EP09802282 A EP 09802282A EP 2307495 B1 EP2307495 B1 EP 2307495B1
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European Patent Office
Prior art keywords
polyethylene
density polyethylene
melt
starch
tps
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EP09802282.5A
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German (de)
French (fr)
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EP2307495A1 (en
EP2307495A4 (en
Inventor
Changping Chen
John Scheirs
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Tristano Pty Ltd
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Tristano Pty Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the present invention relates in general to compositions comprising thermoplastic starch (TPS).
  • TPS thermoplastic starch
  • the invention relates to compositions comprising TPS and polyolefin, to a method of preparing the same, and to products formed therefrom.
  • Starch is attractive in that it is derived from renewal resources (i.e. plant products), readily available and relatively inexpensive.
  • renewal resources i.e. plant products
  • mechanical properties of starch in its native form are quite poor compared with those of petroleum derived (i.e. "synthetic") polymers.
  • the mechanical properties of starch can be improved by melt mixing it with a plasticiser such as a polyhydric alcohol so as to form TPS.
  • a plasticiser such as a polyhydric alcohol
  • the improved mechanical properties of TPS still remain relatively poor compared with those of petroleum derived polymers.
  • Starch or TPS in its own right is therefore not considered a viable alternative to petroleum derived polymers.
  • polyester/TPS blends have been shown to exhibit good mechanical properties and can be formulated so as to be fully biodegradable.
  • hydrolytic sensitivity of the polyester matrix their application can be limited, for example such blends are not generally suited for melt-recycling.
  • Polyolefin/TPS blends e.g. polyethylene/TPS blends
  • polyethylene/TPS blends Due to the non-hydrolytic sensitivity of the polyolefin matrix, such blends are at least expected to be more suited to recycling than their polyester/TPS counterparts.
  • the inherent incompatibility between the highly hydrophobic character of polyolefins and the hydrophilic character TPS has proven problematic in attaining blends with useful properties.
  • US 6,605,657 discloses a method of preparing a polyolefin/TPS blend in which a relatively moisture free TPS is prepared in a first extrusion unit and then as a melt is combined with a polyolefin melt prepared in a second extrusion unit.
  • the resulting blend is said to exhibit good mechanical properties.
  • at least the method by which the blend is made is not without its shortcomings.
  • the present invention therefore provides a composition comprising very low density polyethylene having a density of less than 0.905g/cm 3 , preferably from about 0.85g/cm 3 to 0.905g/cm 3 , ethylene acrylic acid copolymer having a melt index of 190°/2.16 kg ranging from 10 g/10 min to 20 g/10 min, one or more polyethylene polymers having a density of greater than 0.905g/cm 3 , and thermoplastic starch and/or its constituent components thereof
  • compositions in accordance with the invention demonstrate excellent compatibility between the polymeric components as a blend and may be used to provide for polymer products that exhibit excellent properties.
  • compositions in accordance with the invention will comprise about 5-25 wt. % very low density polyethylene (VLDPE), about 5-25 wt. % ethylene acrylic acid copolymer (EAA), and about 50-80 wt. % TPS and/or the constituent components thereof.
  • VLDPE very low density polyethylene
  • EAA ethylene acrylic acid copolymer
  • TPS TPS
  • the composition comprises one or more polyethylene polymers having a density of greater than 0.905g/cm 3 .
  • the one or more polyethylene polymers having a density of greater than 0.905g/cm 3 will generally be present in an amount ranging from about 5-20 wt. %.
  • compositions in accordance with the invention may also further comprise ethylene vinyl acetate copolymer (EVA).
  • EVA ethylene vinyl acetate copolymer
  • the EVA will generally be present in an amount ranging from about 1-10 wt. %.
  • compositions in accordance with the invention are intended to embrace both pre-melt processed (i.e. a physical blend of the components) and post-melt processed (i.e. an integral intimate blend of the components) forms of the compositions. Having said this, it will be appreciated that a composition in accordance with the invention in its pre-melt processed form will generally be prepared for the sole purpose of being subsequently melt processed into a melt processed product.
  • the TPS per se may be present in a pre-melt processed composition, or it can advantageously be prepared in situ from its constituent components during melt processing of the composition.
  • a pre-melt processed composition in accordance with the invention may comprise VLDPE, EAA, TPS and/or the constituent components of the TPS, namely starch and one or more plasticisers.
  • the starch and the one or more plasticisers in the composition will converted into TPS and the resulting melt processed composition will comprise VLDPE, EAA and TPS.
  • the post-melt processed compositions in accordance with the invention it is the intention that any constituent components of TPS in the pre-melt processed composition will be substantially converted into TPS during melt processing.
  • the present invention also provides a method of preparing a polyolefin and thermoplastic starch blend, the method comprising melt processing a composition comprising very low density polyethylene having a density of less than 0.905g/cm 3 , preferably from about 0.85g/cm 3 to 0.905g/cm 3 , ethylene acrylic acid copolymer having a melt index of 190°/2.16 kg ranging from 10 g/10 min to 20 g/10 min, one or more polyethylene polymers having a density of greater than 0.905g/cm 3 , and thermoplastic starch and/or the constituent components thereof.
  • composition that is to be melt processed in accordance with the method of the invention comprise one or more polyethylene polymers having a density greater than 0.905g/cm 3 .
  • the composition that is to be melt processed in accordance with the method of the invention may also comprise EVA.
  • a polyolefin and TPS blend is prepared by melt processing together (1) a polyolefin and TPS blend prepared in accordance with the invention, and (2) one or more polyethylene polymers having a density greater than 0.905g/cm 3 .
  • Melt processed polymer compositions in accordance with the invention have been found to exhibit desirable attributes such as low sensitivity to moisture, a surface amenable to printing, a high content of starch, excellent mechanical properties such as % elongation, and can be readily melt-recycled. Furthermore, such properties can be attained with a relatively high TPS content, which in turn minimises the amount of petroleum derived polymer in the composition.
  • the excellent properties of products formed from compositions in accordance with the invention is believed to stem at least in part from the ability of the compositions to provide the TPS and polyethylene components in a highly compatibilised form.
  • the TPS and polyethylene components of the composition are believed to form stable a co-continuous phase morphology.
  • co-continuous phase morphology in the context of TPS and polyethylene phase domains is intended to mean the topological condition in which a continuous path through either phase domain may be drawn to all phase domain boundaries without crossing any phase domain boundary.
  • co-continuous phase morphology being “stable” is meant that the respective phase domains resist coalescence during or after melt processing.
  • Compositions in accordance with the invention comprise VLDPE having a density of less than 0.905g/cm 3 .
  • the VLDPE will have a density ranging from about 0.85g/cm 3 to 0.905g/cm 3 , for example from about 0.88g/cm 3 to 0.905g/cm 3 .
  • VLDPE is also known in the art as ultra low density polyethylene (ULDPE), and is generally a copolymer of ethylene and one or more alpha-olefins such as 1-butene, 1-hexene, and 1-octene
  • the VLDPE will generally have a melt index at 190°C/2.16kg of about 0.5 g/10 min to about 10 g/10 min
  • Suitable VLDPE that may be used in accordance with the invention includes, but is not limited to, a ethylene/octene copolymer having a density of about 0.904g/cm 3 and a melt index at 190°C/2.16kg of about 4g/10 min, and ethylene/butene copolymer having a density of about 0.884g/cm 3 and a melt index at 190°C/2.16kg of about 0.7g/10 min, and an ethylene/butene copolymer having a density of about 0.8985 and melt index at 190°C/2.16kg of about 5g/10 min.
  • a density or melt index of a polyethylene polymer is intended to mean a density or melt index determined in accordance with ASTM D792 and ASTM D1238, respectively.
  • Compositions in accordance with the invention also comprise EAA having a melt index of 190°C/2.16kg ranging from about 10 g/10 min to about 20 g/10 min.
  • EAA is a copolymer of ethylene and acrylic acid. Generally, the acrylic acid content of the copolymer will range from about 5-20%, for example 8-15%.
  • Suitable grades of VLDPE and EAA for use in accordance with the invention may be obtained commercially.
  • compositions in accordance with the invention further comprise TPS and/or the constituent components thereof.
  • TPS is a destructured form of starch comprising one or more plasticisers. Accordingly, as used herein, the expression "constituent components thereof" in the context of TPS is intended to mean the individual ingredients that are used to prepare the TPS.
  • Starch is found chiefly in seeds, fruits, tubers, roots and stem pith of plants, and is a naturally derived polymer made up of repeating glucose groups linked by glucosidic linkages in the 1-4 carbon positions.
  • Starch consists of two types of alpha-D-glucose polymers: amylose, a substantially linear polymer with molecular weight of about 1 x 10 5 ; and amylopectin, a highly branched polymer with very high molecular weight of the order 1 x 10 7 .
  • Each repeating glucose unit typically has three free hydroxyl groups, thereby providing the polymer with hydrophilic properties and reactive functional groups.
  • Most starches contain 20 to 30% amylose and 70 to 80% amylopectin.
  • amylose to amylopectin can vary significantly.
  • some corn hybrids provide starch with 100% amylopectin (waxy corn starch), or progressively higher amylose content ranging from 50 to 95%.
  • Starch usually has a water content of about 15wt.%.
  • the starch can be dried to reduce its water content to below 1%.
  • Starch typically exists in small granules having a crystallinity ranging from about 15 to 45%.
  • the size of the granules may vary depending upon the origin of the starch. For example, corn starch typically has a particle size diameter ranging from about 5 ⁇ m to about 40 ⁇ m, whereas potato starch typically has a particle size diameter ranging from about 50 ⁇ m to about 100 ⁇ m.
  • This "native" form of starch may also be chemically modified.
  • Chemically modified starch includes, but is not limited to, oxidised starch, etherificated starch, esterified starch, crosslinked starch or a combination of such chemical modifications (e.g. etherificated and esterified starch).
  • Chemically modified starch is generally prepared by reacting the hydroxyl groups of starch with one or more reagents. The degree of reaction, often referred to as the degree of substitution (DS), can significantly alter the physiochemical properties of the modified starch compared with the corresponding native starch.
  • the DS for a native starch is designated as 0 and can range up to 3 for a fully substituted modified starch.
  • a chemically modified starch can exhibit considerably different hydrophilic/hydrophobic character relative to native starch.
  • Both native and chemically modified starch generally exhibit poor thermoplastic properties.
  • the starch may be converted to TPS by means well known in the art.
  • native or chemically modified starch may be melt processed with one or more plasticisers.
  • Polyhydric alcohols are generally used as plasticisers in the manufacture of TPS.
  • TPS wt. %
  • the starch from which the TPS may be derived includes, but is not limited to, corn starch, potato starch, wheat starch, soy bean starch, tapioca starch, hi-amylose starch or combinations thereof.
  • starch is chemically modified, it will generally be etherificated or esterified.
  • Suitable etherificated starches include, but are not limited to, those which are substituted with ethyl and/or propyl groups.
  • Suitable esterified starches include, but are not limited to, those that are substituted with actyl, propanoyl and/or butanoyl groups.
  • the starch used to prepare the TPS is corn starch or corn starch acetate having a DS > 0.1.
  • the TPS will generally also comprise one or more polyhydric alcohol plasticisers.
  • Suitable polyhydric alcohols include, but are not limited to glycerol, ethylene glycol, propylene glycol, ethylene diglycol, propylene diglycol, ethylene triglycol, propylene triglycol, polyethylene glycol, polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,2,6-hexanetriol, 1,3,5-hexanetriol, neo-pentyl glycol, trimethylol propane, pentaerythritol, mannitol, sorbitol, and the acetate, ethoxylate, and prop
  • the TPS comprises glycerol and/or sorbitol plasticisers.
  • the plasticiser content of the TPS will generally range from about 5 wt. % to about 50 wt. %, for example from about 10 wt. % to about 40 wt. %, or from about 10 wt. % to about 30 wt. %, relative to the combined mass of the starch and plasticiser components
  • compositions in accordance with the invention may be provided in the form of a pre-melt processed composition or a post-melt processed composition.
  • compositions in accordance with the invention provided in a pre-melt processed form
  • the compositions will generally be prepared so as to ultimately be melt processed and form a melt processed blend of the individual components therein.
  • some or all of TPS can advantageously be replaced by the constituent components used to prepare TPS (i.e. starch and one or more plasticisers).
  • starch and one or more plasticisers can be melt processed in the presence of the VLDPE and EAA so as to produce a melt processed composition comprising VLDPE, EAA and TPS.
  • Compositions in accordance with the invention will generally comprise the VLDPE in an amount ranging from about 5 wt. % to about 25 wt. %, for example about 15 wt. %, the EAA in an amount ranging from about 5 wt. % to about 25 wt. %, for example about 15 wt. %, and the TPS and/or the constituent components thereof in an amount ranging from about 50 wt. % to about 80 wt. %, for example about 70 wt. %.
  • compositions in accordance with the invention comprise constituent components of TPS
  • the total mass of these components may be considered equivalent to the mass of TPS per se and therefore the same weight percent ranges for the TPS outlined herein apply to these collective components.
  • the relative weight percent ranges for each component of the TPS are also outlined herein.
  • compositions in accordance with the invention also comprise one or more polyethylene polymers having a density greater than 0.905g/cm 3 .
  • the composition may comprise low density polyethylene (LDPE) which is generally characterised as having a density in the range of 0.910 to 0.940g/cm 3 .
  • LDPE low density polyethylene
  • Suitable grades of LDPE include, but are not limited to, those having a melt index at 190°C/2.16kg of about 0.2g/10 min to about 7g/10 min.
  • compositions may comprise linear low density polyethylene (LLDPE) which is generally characterised as having a density ranging from 0.915g/cm 3 to 0.925g/cm 3 , medium density polyethylene (MDPE) which is generally characterised as having a density ranging from 0.926g/cm 3 to 0.940g/cm 3 , and/or high density polyethylene (HDPE) which is generally characterised as having a density of greater or equal to 0.941g/cm 3 .
  • LLDPE linear low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • Suitable grades of LDPE, LLDPE, MDPE and HDPE for use in accordance with the invention may be obtained commercially.
  • the one or more polyethylene polymers having a density greater than 0.905g/cm 3 will generally be present in the compositions in an amount ranging from about 5 wt. % to about 20 wt. %.
  • compositions in accordance with the invention may comprise VLDPE in an amount of about 10 wt. %, EAA in an amount of about 10 wt. %, TPS and/or the constituent components thereof in an amount of about 65 wt. %, and LDPE in an amount of about 15 wt. %.
  • compositions in accordance with the invention may also comprise EVA in an amount ranging from about 1 wt. % to about 10 wt. %.
  • the composition may comprise VLDPE in an amount of about 10 wt. %, EAA in an amount of about 10 wt. %, TPS and/or the constituent components thereof in an amount of about 65 wt. %, LDPE in an amount of about 10 wt. %, and EVA in an amount of about 5 wt. %.
  • compositions in accordance with the invention may also comprise one or more additives.
  • Such additives may include fillers (e.g. calcium carbonate, talc, clays (e.g. montmorillonite), and titanium dioxide); pigments; anti-static agents; and processing aids (e.g. calcium stearate, steric acid, magnesium stearate, sodium stearate, oxidised polyethylene, oleamide, stearamide and erucamide).
  • fillers e.g. calcium carbonate, talc, clays (e.g. montmorillonite), and titanium dioxide
  • pigments e.g. calcium carbonate, talc, clays (e.g. montmorillonite), and titanium dioxide
  • pigments e.g. calcium stearate, steric acid, magnesium stearate, sodium stearate, oxidised polyethylene, oleamide, stearamide and erucamide.
  • processing aids e.g. calcium stearate, steric acid, magnesium stearate, sodium stearate, oxidised poly
  • the additives will be used in an amount ranging from about 0.5 wt. % to about 2 wt. %.
  • compositions in accordance with the invention provided in the form of a melt processed blend can be prepared according to the method of the invention.
  • a polyolefin and TPS blend is prepared by melt processing a composition comprising VLDPE, EAA, one or more polyethylene polymers having a density of greater than 0.905g/cm 3 , and TPS and/or the constituent components thereof.
  • melt processing may be performed using techniques and equipment well known in the art. Generally, melt processing is achieved using continuous extrusion equipment, such as single screw extruders, twin screw extruders, other multiple screw extruders or Farrell continuous mixers. Melt processing is conducted for sufficient time and at a suitable temperature to promote intimate blending between the components of the composition. Those skilled in the art will appreciate that melt processing is generally performed within a suitable temperature range that this range will vary depending upon the nature of the polymer(s) being processed. Generally, the compositions in accordance with the invention will be melt processed at temperatures ranging from about 150°C to about 210°C.
  • composition that is to be melt processed comprises the constituent components of TPS
  • the method in accordance with the invention advantageously converts these components during melt processing into TPS.
  • the composition to be melt processed in accordance with the method of the invention may be first physically blended in a high speed mixer.
  • the method may first comprise blending in a high speed mixer in the following order of addition starch, EAA, VLDPE and one or more polyhydric alcohols such as glycerol and/or sorbitol.
  • the one or more polyethylene polymers having a density greater than 0.905g/cm 3 may be added directly after the VLDPE.
  • EVA is used in the composition, it may be added directly after all the polyethylene polymers have been added.
  • one or more additives are used in the composition, they may be added directly before the one or more plasticisers.
  • compositions in accordance with the invention comprise one or more polyethylene polymers having a density greater than 0.905g/cm 3 .
  • This polyethylene component(s) may form part of the composition that is melt processed in accordance with the method of the invention, or some or all of it may be introduced as part of a second melt processing step.
  • a polyolefin and TPS blend prepared in accordance with the method of the invention may be subsequently combined together with a polyethylene polymer having a density greater than 0.905g/cm 3 and the mixture melt processed so as to incorporate further polyethylene polymer into the blend.
  • the method comprises melt processing the so formed polyolefin and TPS blend with one or more polyethylene polymers having a density greater than 0.905g/cm 3 .
  • about 40 wt. % to about 60 wt. % of the so formed polyolefin and TPS blend will generally be melt processed with about 60 wt. % to about 40 wt. % of one or more polyethylene polymers having a density greater than 0.905g/cm 3 .
  • the polyolefin and TPS blend in accordance with the invention have been found to exhibit a number of advantageous properties relative to a conventional polyolefin / TPS blend.
  • the blend in accordance with the invention demonstrates excellent % elongation even at high (e.g. about 40-50 weight %) TPS loadings. Products such as films formed from the composition can therefore exhibit improved puncture and tear resistance.
  • the blend may also exhibit decreased sensitivity to moisture and a surface that is particularly suited for printing without being subjected to surface modification techniques such as coroner treatment.
  • the blends can demonstrate a wettable surface (e.g. having a surface polarity equivalent to about 42-55 dynes) without being subject to surface treatments. Film formed from the composition can therefore be printed without first having to be subjected to surface treatment.
  • the blend in accordance with the invention is well suited for melt-recycling.
  • the polyolefin and TPS blend in accordance with the invention is well suited for manufacturing films and moulded products. Such products can readily be used in many applications such as packaging.
  • the improved properties afforded by the blend in accordance with the invention is least in part due to the TPS and polyethylene phase domains of the blend being highly compatibilised.
  • the TPS and polyethylene phase domains can be provided with a co-continuous morphology.
  • the high degree of compatibility between the polyethylene and TPS phases domains is believed to result from the unique blend of VLDPE in combination with EAA and TPS.
  • composition A The components listed below in Table 1 (composition A) were first blended in a high speed mixer in the following order of addition: starch, EAA, VLDPE, LDPE, Calcium stearate, stearic acid, glycerol, and sorbitol. The resulting physical blend was then melt processed on a vented twin screw extruder having melt profile 140/170/175/175/165/155 deg.C, torque ⁇ 80%, screw speed 320-350 rpm, vacuum of -0.05 bar and output of 200 kg/h to provide for Blend A. Film was then blown from a composition of 50 wt. % Blend A and 50 wt. % LLDPE.
  • the resulting film had a gauge of 15 micron, a tensile strength at break of 14 MPa, and an elongation of > 200% as tested using a universal tensile testing machine.
  • Table 1 Composition A Component Grade and Supplier Amount % Cornstarch Grade: Eatable or industry first class products 50kg/100.8kg 49.60 Supplier: Shandong Zhucheng Starch Pty Ltd. Degree of Substitution: >0.1 Glycerol Grade: saponification Glycerol or vegetal 11kg/100.8kg 10.91 Glycerol Supplier: Nanjing Soap factory Purity: ⁇ 96% Boiling Point: >250 deg.
  • composition B The components listed below in Table 2 (composition B) were first blended in a high speed mixer in the following order of addition: starch, LDPE, VLDPE, EAA, Calcium stearate, stearic acid, glycerol, and sorbitol. The resulting physical blend was then melt processed on a vented twin screw extruder having melt profile 140/170/175/175/165/155 deg.C, torque ⁇ 80%, screw speed 320-350 rpm, vacuum of -0.05 bar and output of 200 kg/h to provide for Blend B. Film was then blown using Blend B.
  • the resulting film had a tensile strength at break of greater than 10 MPa, and an elongation of > 250% as tested using a universal tensile testing machine.
  • the film exhibited excellent antiblock and anti-static properties.
  • Table 2 Composition B Component Grade and Supplier Amount % Cornstarch Grade: Eatable or industry first class products 42kg/100.8kg 41.66 Supplier: Shandong Zhucheng Starch Pty Ltd. Degree of Substitution: >0.1
  • Glycerol Grade saponification Glycerol or vegetal 11kg/100.8kg 10.91
  • Glycerol Supplier Nanjing Soap factory Purity: ⁇ 96% Boiling Point: >250 deg.
  • composition C The components listed below in Table 3 (composition C) were first blended in a high speed mixer in the following order of addition: starch, EAA, VLDPE, EVA LDPE, Calcium stearate, stearic acid, glycerol, and sorbitol. The resulting physical blend was then melt processed on a vented twin screw extruder having melt profile 140/165/170/170/170/155 deg.C, torque ⁇ 80%, screw speed 320-350 rpm, vacuum of -0.05 bar and output of 200 kg/h to provide for Blend C. Blend C was formed into a foam buy melt processing it with a conventional blowing agent masterbatch. The resulting foam is suitable as a soft foam packaging material and has excellent softness and soft touch properties.
  • Table 3 Composition C Ingredient Grade and Supplier Amount % Cornstarch Grade: Eatable or industry first class products 50kg/105.8kg 47.23 Supplier: Shandong Zhucheng Starch Pty Ltd. Degree of Substitution: >0.1 Glycerol Grade: saponification Glycerol or vegetal Glycerol 11kg/105.8kg 10.42 Supplier: Nanjing Soap factory Purity: ⁇ 96% Boiling Point: >250 deg. C Sorbitol Grade: industry Sorbitol 5kg/105.8kg 4.72 Supplier: Jiangsu Luo'er Gaici Pty Ltd.
  • Blend B was melt processed with 20 wt. % LDPE (melt index 0.3g/10 mins and density of 0.922 g/cm 3 ) and formed into sheet of 0.380 mm thickness. The resulting sheet was thermoformed into a cuspated sheet.
  • Blend B was blown into 50 micron film and then converted into shopping bags with a loading carrying capacity of 6 kg.
  • the bags were found to have comparable tear, tensile and elongational properties to bags made from HDPE.
  • the film can be easily printed using conventional processes and without Corona pre-treatment.
  • Blend B was melt processed with 10 wt. % HDPE and blown into a film suitable for use in shopping bag applications. The resulting film was found to be 100% more stiff than a comparable film made from just Blend B.

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Description

    FIELD OF THE INVENTION
  • The present invention relates in general to compositions comprising thermoplastic starch (TPS). In particular, the invention relates to compositions comprising TPS and polyolefin, to a method of preparing the same, and to products formed therefrom.
    • BACKGROUND OF THE INVENTION
  • With an ever increasing emphasis on sustainability and the environment, there has been a corresponding increase in research directed toward developing polymeric materials derived from or comprising renewable biologically derived components.
  • Much of the research to date in developing such polymeric materials has focussed on utilising naturally occurring bio-polymers such as starch. Starch is attractive in that it is derived from renewal resources (i.e. plant products), readily available and relatively inexpensive. However, the mechanical properties of starch in its native form are quite poor compared with those of petroleum derived (i.e. "synthetic") polymers.
  • The mechanical properties of starch can be improved by melt mixing it with a plasticiser such as a polyhydric alcohol so as to form TPS. However, the improved mechanical properties of TPS still remain relatively poor compared with those of petroleum derived polymers.
  • Starch or TPS in its own right is therefore not considered a viable alternative to petroleum derived polymers.
  • In attempt to derive the benefits of starch and petroleum derived polymers, a considerable amount or research has been directed toward developing blends of these two polymer materials. However, combining relatively hydrophilic starch with petroleum derived polymers, which are typically hydrophobic, to produce blends with good mechanical properties has proven difficult in practice. In particular, melt processing starch or TPS with petroleum derived polymers generally results in the formation of polymer blends having a multi-phase discontinuous morphology. Such morphologies are typically unstable and exhibit high interfacial tension, the like of which often has a negative impact on at least the mechanical properties of the resulting polymer blend.
  • Nevertheless, useful blends of starch or TPS and petroleum derived polymers have been developed. For example, polyester/TPS blends have been shown to exhibit good mechanical properties and can be formulated so as to be fully biodegradable. However, due to the hydrolytic sensitivity of the polyester matrix their application can be limited, for example such blends are not generally suited for melt-recycling.
  • Polyolefin/TPS blends (e.g. polyethylene/TPS blends) have also been developed. Due to the non-hydrolytic sensitivity of the polyolefin matrix, such blends are at least expected to be more suited to recycling than their polyester/TPS counterparts. However, the inherent incompatibility between the highly hydrophobic character of polyolefins and the hydrophilic character TPS has proven problematic in attaining blends with useful properties.
  • US 6,605,657 discloses a method of preparing a polyolefin/TPS blend in which a relatively moisture free TPS is prepared in a first extrusion unit and then as a melt is combined with a polyolefin melt prepared in a second extrusion unit. The resulting blend is said to exhibit good mechanical properties. However, at least the method by which the blend is made is not without its shortcomings.
  • While polymer blends comprising both TPS and petroleum derived polymers have been developed, and opportunity remains to address or ameliorate one or more disadvantage or shortcoming associated with such blends and/or the methods by which such blends are prepared, or to at least provide a useful alternative polymer blend and/or method for preparing it.
    • SUMMARY OF THE INVENTION
  • The present invention therefore provides a composition comprising very low density polyethylene having a density of less than 0.905g/cm3, preferably from about 0.85g/cm3 to 0.905g/cm3, ethylene acrylic acid copolymer having a melt index of 190°/2.16 kg ranging from 10 g/10 min to 20 g/10 min, one or more polyethylene polymers having a density of greater than 0.905g/cm3, and thermoplastic starch and/or its constituent components thereof
  • It has now been found that compositions in accordance with the invention demonstrate excellent compatibility between the polymeric components as a blend and may be used to provide for polymer products that exhibit excellent properties.
  • Generally, the compositions in accordance with the invention will comprise about 5-25 wt. % very low density polyethylene (VLDPE), about 5-25 wt. % ethylene acrylic acid copolymer (EAA), and about 50-80 wt. % TPS and/or the constituent components thereof.
  • The composition comprises one or more polyethylene polymers having a density of greater than 0.905g/cm3. The one or more polyethylene polymers having a density of greater than 0.905g/cm3 will generally be present in an amount ranging from about 5-20 wt. %.
  • In addition to the one or more polyethylene polymers having a density of greater than 0.905g/cm3, the compositions in accordance with the invention may also further comprise ethylene vinyl acetate copolymer (EVA). In that case, the EVA will generally be present in an amount ranging from about 1-10 wt. %.
  • The compositions in accordance with the invention are intended to embrace both pre-melt processed (i.e. a physical blend of the components) and post-melt processed (i.e. an integral intimate blend of the components) forms of the compositions. Having said this, it will be appreciated that a composition in accordance with the invention in its pre-melt processed form will generally be prepared for the sole purpose of being subsequently melt processed into a melt processed product.
  • The TPS per se may be present in a pre-melt processed composition, or it can advantageously be prepared in situ from its constituent components during melt processing of the composition. Accordingly, a pre-melt processed composition in accordance with the invention may comprise VLDPE, EAA, TPS and/or the constituent components of the TPS, namely starch and one or more plasticisers. Upon being melt processed, the starch and the one or more plasticisers in the composition will converted into TPS and the resulting melt processed composition will comprise VLDPE, EAA and TPS. In other words, in post-melt processed compositions in accordance with the invention it is the intention that any constituent components of TPS in the pre-melt processed composition will be substantially converted into TPS during melt processing.
  • The present invention also provides a method of preparing a polyolefin and thermoplastic starch blend, the method comprising melt processing a composition comprising very low density polyethylene having a density of less than 0.905g/cm3, preferably from about 0.85g/cm3 to 0.905g/cm3, ethylene acrylic acid copolymer having a melt index of 190°/2.16 kg ranging from 10 g/10 min to 20 g/10 min, one or more polyethylene polymers having a density of greater than 0.905g/cm3, and thermoplastic starch and/or the constituent components thereof.
  • The composition that is to be melt processed in accordance with the method of the invention comprise one or more polyethylene polymers having a density greater than 0.905g/cm3. In addition to the one or more polyethylene polymers having a density greater than 0.905g/cm3, the composition that is to be melt processed in accordance with the method of the invention may also comprise EVA.
  • In one embodiment of the invention, a polyolefin and TPS blend is prepared by melt processing together (1) a polyolefin and TPS blend prepared in accordance with the invention, and (2) one or more polyethylene polymers having a density greater than 0.905g/cm3.
  • Melt processed polymer compositions in accordance with the invention have been found to exhibit desirable attributes such as low sensitivity to moisture, a surface amenable to printing, a high content of starch, excellent mechanical properties such as % elongation, and can be readily melt-recycled. Furthermore, such properties can be attained with a relatively high TPS content, which in turn minimises the amount of petroleum derived polymer in the composition.
  • Without wishing to be limited by theory, the excellent properties of products formed from compositions in accordance with the invention is believed to stem at least in part from the ability of the compositions to provide the TPS and polyethylene components in a highly compatibilised form. In some embodiments of the invention, the TPS and polyethylene components of the composition are believed to form stable a co-continuous phase morphology.
  • Further aspects of the invention are described in more detail below.
    • DETAILED DESCRIPTION OF THE INVENTION
  • As used herein, the expression "co-continuous phase morphology" in the context of TPS and polyethylene phase domains is intended to mean the topological condition in which a continuous path through either phase domain may be drawn to all phase domain boundaries without crossing any phase domain boundary. By the co-continuous phase morphology being "stable" is meant that the respective phase domains resist coalescence during or after melt processing.
  • Compositions in accordance with the invention comprise VLDPE having a density of less than 0.905g/cm3. Generally, the VLDPE will have a density ranging from about 0.85g/cm3 to 0.905g/cm3, for example from about 0.88g/cm3 to 0.905g/cm3. VLDPE is also known in the art as ultra low density polyethylene (ULDPE), and is generally a copolymer of ethylene and one or more alpha-olefins such as 1-butene, 1-hexene, and 1-octene
  • The VLDPE will generally have a melt index at 190°C/2.16kg of about 0.5 g/10 min to about 10 g/10 min
  • Suitable VLDPE that may be used in accordance with the invention includes, but is not limited to, a ethylene/octene copolymer having a density of about 0.904g/cm3 and a melt index at 190°C/2.16kg of about 4g/10 min, and ethylene/butene copolymer having a density of about 0.884g/cm3 and a melt index at 190°C/2.16kg of about 0.7g/10 min, and an ethylene/butene copolymer having a density of about 0.8985 and melt index at 190°C/2.16kg of about 5g/10 min.
  • Reference herein to a density or melt index of a polyethylene polymer is intended to mean a density or melt index determined in accordance with ASTM D792 and ASTM D1238, respectively.
  • Compositions in accordance with the invention also comprise EAA having a melt index of 190°C/2.16kg ranging from about 10 g/10 min to about 20 g/10 min. Those skilled in the art will appreciate that EAA is a copolymer of ethylene and acrylic acid. Generally, the acrylic acid content of the copolymer will range from about 5-20%, for example 8-15%.
  • Suitable grades of VLDPE and EAA for use in accordance with the invention may be obtained commercially.
  • The compositions in accordance with the invention further comprise TPS and/or the constituent components thereof. Those skilled in the art will appreciate that TPS is a destructured form of starch comprising one or more plasticisers. Accordingly, as used herein, the expression "constituent components thereof" in the context of TPS is intended to mean the individual ingredients that are used to prepare the TPS.
  • Starch is found chiefly in seeds, fruits, tubers, roots and stem pith of plants, and is a naturally derived polymer made up of repeating glucose groups linked by glucosidic linkages in the 1-4 carbon positions. Starch consists of two types of alpha-D-glucose polymers: amylose, a substantially linear polymer with molecular weight of about 1 x 105; and amylopectin, a highly branched polymer with very high molecular weight of the order 1 x 107. Each repeating glucose unit typically has three free hydroxyl groups, thereby providing the polymer with hydrophilic properties and reactive functional groups. Most starches contain 20 to 30% amylose and 70 to 80% amylopectin. However, depending on the origin of the starch the ratio of amylose to amylopectin can vary significantly. For example, some corn hybrids provide starch with 100% amylopectin (waxy corn starch), or progressively higher amylose content ranging from 50 to 95%. Starch usually has a water content of about 15wt.%. However, the starch can be dried to reduce its water content to below 1%.
  • Starch typically exists in small granules having a crystallinity ranging from about 15 to 45%. The size of the granules may vary depending upon the origin of the starch. For example, corn starch typically has a particle size diameter ranging from about 5 µm to about 40µm, whereas potato starch typically has a particle size diameter ranging from about 50µm to about 100µm.
  • This "native" form of starch may also be chemically modified. Chemically modified starch includes, but is not limited to, oxidised starch, etherificated starch, esterified starch, crosslinked starch or a combination of such chemical modifications (e.g. etherificated and esterified starch). Chemically modified starch is generally prepared by reacting the hydroxyl groups of starch with one or more reagents. The degree of reaction, often referred to as the degree of substitution (DS), can significantly alter the physiochemical properties of the modified starch compared with the corresponding native starch. The DS for a native starch is designated as 0 and can range up to 3 for a fully substituted modified starch. Depending upon the type of substituent and the DS, a chemically modified starch can exhibit considerably different hydrophilic/hydrophobic character relative to native starch.
  • Both native and chemically modified starch generally exhibit poor thermoplastic properties. To improve such properties, the starch may be converted to TPS by means well known in the art. For example, native or chemically modified starch may be melt processed with one or more plasticisers. Polyhydric alcohols are generally used as plasticisers in the manufacture of TPS.
  • Reference herein to the wt. % of TPS is therefore intended to include the collective mass of both the starch and plasticiser constituent components of the TPS.
  • The starch from which the TPS may be derived includes, but is not limited to, corn starch, potato starch, wheat starch, soy bean starch, tapioca starch, hi-amylose starch or combinations thereof.
  • Where the starch is chemically modified, it will generally be etherificated or esterified. Suitable etherificated starches include, but are not limited to, those which are substituted with ethyl and/or propyl groups. Suitable esterified starches include, but are not limited to, those that are substituted with actyl, propanoyl and/or butanoyl groups.
  • In one embodiment of the invention, the starch used to prepare the TPS is corn starch or corn starch acetate having a DS > 0.1.
  • The TPS will generally also comprise one or more polyhydric alcohol plasticisers. Suitable polyhydric alcohols include, but are not limited to glycerol, ethylene glycol, propylene glycol, ethylene diglycol, propylene diglycol, ethylene triglycol, propylene triglycol, polyethylene glycol, polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,2,6-hexanetriol, 1,3,5-hexanetriol, neo-pentyl glycol, trimethylol propane, pentaerythritol, mannitol, sorbitol, and the acetate, ethoxylate, and propoxylate derivatives thereof.
  • In one embodiment, the TPS comprises glycerol and/or sorbitol plasticisers.
  • The plasticiser content of the TPS will generally range from about 5 wt. % to about 50 wt. %, for example from about 10 wt. % to about 40 wt. %, or from about 10 wt. % to about 30 wt. %, relative to the combined mass of the starch and plasticiser components
  • Compositions in accordance with the invention may be provided in the form of a pre-melt processed composition or a post-melt processed composition.
  • Where the compositions in accordance with the invention provided in a pre-melt processed form, it will be appreciated that the compositions will generally be prepared so as to ultimately be melt processed and form a melt processed blend of the individual components therein. In that case, some or all of TPS can advantageously be replaced by the constituent components used to prepare TPS (i.e. starch and one or more plasticisers). In particular, it has been found that starch and one or more plasticisers can be melt processed in the presence of the VLDPE and EAA so as to produce a melt processed composition comprising VLDPE, EAA and TPS.
  • Compositions in accordance with the invention will generally comprise the VLDPE in an amount ranging from about 5 wt. % to about 25 wt. %, for example about 15 wt. %, the EAA in an amount ranging from about 5 wt. % to about 25 wt. %, for example about 15 wt. %, and the TPS and/or the constituent components thereof in an amount ranging from about 50 wt. % to about 80 wt. %, for example about 70 wt. %.
  • Where the compositions in accordance with the invention comprise constituent components of TPS, the total mass of these components may be considered equivalent to the mass of TPS per se and therefore the same weight percent ranges for the TPS outlined herein apply to these collective components. The relative weight percent ranges for each component of the TPS are also outlined herein.
  • Compositions in accordance with the invention also comprise one or more polyethylene polymers having a density greater than 0.905g/cm3. For example, the composition may comprise low density polyethylene (LDPE) which is generally characterised as having a density in the range of 0.910 to 0.940g/cm3. Suitable grades of LDPE include, but are not limited to, those having a melt index at 190°C/2.16kg of about 0.2g/10 min to about 7g/10 min.
  • In addition to or separate from LDPE, compositions may comprise linear low density polyethylene (LLDPE) which is generally characterised as having a density ranging from 0.915g/cm3 to 0.925g/cm3, medium density polyethylene (MDPE) which is generally characterised as having a density ranging from 0.926g/cm3 to 0.940g/cm3, and/or high density polyethylene (HDPE) which is generally characterised as having a density of greater or equal to 0.941g/cm3.
  • Suitable grades of LDPE, LLDPE, MDPE and HDPE for use in accordance with the invention may be obtained commercially.
  • The one or more polyethylene polymers having a density greater than 0.905g/cm3 will generally be present in the compositions in an amount ranging from about 5 wt. % to about 20 wt. %.
  • For example, the compositions in accordance with the invention may comprise VLDPE in an amount of about 10 wt. %, EAA in an amount of about 10 wt. %, TPS and/or the constituent components thereof in an amount of about 65 wt. %, and LDPE in an amount of about 15 wt. %.
  • In addition to the one or more polyethylene polymers having a density greater than 0.905g/cm3, the compositions in accordance with the invention may also comprise EVA in an amount ranging from about 1 wt. % to about 10 wt. %.
  • For example, the composition may comprise VLDPE in an amount of about 10 wt. %, EAA in an amount of about 10 wt. %, TPS and/or the constituent components thereof in an amount of about 65 wt. %, LDPE in an amount of about 10 wt. %, and EVA in an amount of about 5 wt. %.
  • Compositions in accordance with the invention may also comprise one or more additives.
  • Such additives may include fillers (e.g. calcium carbonate, talc, clays (e.g. montmorillonite), and titanium dioxide); pigments; anti-static agents; and processing aids (e.g. calcium stearate, steric acid, magnesium stearate, sodium stearate, oxidised polyethylene, oleamide, stearamide and erucamide).
  • Generally, the additives will be used in an amount ranging from about 0.5 wt. % to about 2 wt. %.
  • Compositions in accordance with the invention provided in the form of a melt processed blend can be prepared according to the method of the invention.
  • Thus, according to the method of the invention a polyolefin and TPS blend is prepared by melt processing a composition comprising VLDPE, EAA, one or more polyethylene polymers having a density of greater than 0.905g/cm3, and TPS and/or the constituent components thereof.
  • Melt processing may be performed using techniques and equipment well known in the art. Generally, melt processing is achieved using continuous extrusion equipment, such as single screw extruders, twin screw extruders, other multiple screw extruders or Farrell continuous mixers. Melt processing is conducted for sufficient time and at a suitable temperature to promote intimate blending between the components of the composition. Those skilled in the art will appreciate that melt processing is generally performed within a suitable temperature range that this range will vary depending upon the nature of the polymer(s) being processed. Generally, the compositions in accordance with the invention will be melt processed at temperatures ranging from about 150°C to about 210°C.
  • As indicated above, where the composition that is to be melt processed comprises the constituent components of TPS, the method in accordance with the invention advantageously converts these components during melt processing into TPS.
  • The composition to be melt processed in accordance with the method of the invention may be first physically blended in a high speed mixer. For example, the method may first comprise blending in a high speed mixer in the following order of addition starch, EAA, VLDPE and one or more polyhydric alcohols such as glycerol and/or sorbitol. The one or more polyethylene polymers having a density greater than 0.905g/cm3 may be added directly after the VLDPE. Where EVA is used in the composition, it may be added directly after all the polyethylene polymers have been added. Where one or more additives are used in the composition, they may be added directly before the one or more plasticisers.
  • The compositions in accordance with the invention comprise one or more polyethylene polymers having a density greater than 0.905g/cm3. This polyethylene component(s) may form part of the composition that is melt processed in accordance with the method of the invention, or some or all of it may be introduced as part of a second melt processing step. For example, a polyolefin and TPS blend prepared in accordance with the method of the invention may be subsequently combined together with a polyethylene polymer having a density greater than 0.905g/cm3 and the mixture melt processed so as to incorporate further polyethylene polymer into the blend.
  • Thus, in one embodiment of the invention the method comprises melt processing the so formed polyolefin and TPS blend with one or more polyethylene polymers having a density greater than 0.905g/cm3. In that case, about 40 wt. % to about 60 wt. % of the so formed polyolefin and TPS blend will generally be melt processed with about 60 wt. % to about 40 wt. % of one or more polyethylene polymers having a density greater than 0.905g/cm3.
  • The polyolefin and TPS blend in accordance with the invention have been found to exhibit a number of advantageous properties relative to a conventional polyolefin / TPS blend. For example, the blend in accordance with the invention demonstrates excellent % elongation even at high (e.g. about 40-50 weight %) TPS loadings. Products such as films formed from the composition can therefore exhibit improved puncture and tear resistance. The blend may also exhibit decreased sensitivity to moisture and a surface that is particularly suited for printing without being subjected to surface modification techniques such as coroner treatment. In particular, the blends can demonstrate a wettable surface (e.g. having a surface polarity equivalent to about 42-55 dynes) without being subject to surface treatments. Film formed from the composition can therefore be printed without first having to be subjected to surface treatment. Furthermore, the blend in accordance with the invention is well suited for melt-recycling.
  • The polyolefin and TPS blend in accordance with the invention is well suited for manufacturing films and moulded products. Such products can readily be used in many applications such as packaging.
  • Without wishing to be limited by theory, it is believed that the improved properties afforded by the blend in accordance with the invention is least in part due to the TPS and polyethylene phase domains of the blend being highly compatibilised. In particular, it is believed that the TPS and polyethylene phase domains can be provided with a co-continuous morphology. The high degree of compatibility between the polyethylene and TPS phases domains is believed to result from the unique blend of VLDPE in combination with EAA and TPS.
  • Embodiments of the invention are further described with reference to the following nonlimiting examples.
    • EXAMPLES Example 1
  • The components listed below in Table 1 (composition A) were first blended in a high speed mixer in the following order of addition: starch, EAA, VLDPE, LDPE, Calcium stearate, stearic acid, glycerol, and sorbitol. The resulting physical blend was then melt processed on a vented twin screw extruder having melt profile 140/170/175/175/165/155 deg.C, torque < 80%, screw speed 320-350 rpm, vacuum of -0.05 bar and output of 200 kg/h to provide for Blend A. Film was then blown from a composition of 50 wt. % Blend A and 50 wt. % LLDPE. The resulting film had a gauge of 15 micron, a tensile strength at break of 14 MPa, and an elongation of > 200% as tested using a universal tensile testing machine. Table 1: Composition A
    Component Grade and Supplier Amount %
    Cornstarch Grade: Eatable or industry first class products 50kg/100.8kg 49.60
    Supplier: Shandong Zhucheng Starch Pty Ltd.
    Degree of Substitution: >0.1
    Glycerol Grade: saponification Glycerol or vegetal 11kg/100.8kg 10.91
    Glycerol
    Supplier: Nanjing Soap factory
    Purity: ≥96%
    Boiling Point: >250 deg. C
    Sorbitol Grade: industry Sorbitol 5 kg/100.8kg 4.96
    Supplier: Jiangsu Luo'er Gaici Pty Ltd.
    Purity: ≥70%
    Boiling Point: ≈100 deg.C
    EAA Grade: Primacor 3340 12kg/100.8kg 11.91
    Supplier: DOW
    MFI: 10.5 g/10mins (190 deg. C/2.16kg)
    Density: 0.938g/cm3
    ethylene-acrylic acid copolymer having an
    acrylic acid content of 9.5%
    VLDPE Grade: Attane 4404 10kg/100.8kg 9.92
    Supplier: DOW
    MFI: 4g/10mins (190 deg. C, 2.16kg)
    Density: 0.904 g/cm3
    LDPE Grade: 1FTB 12kg/100.8 kg 11.91
    Supplier: Beijing Yanshan Pty Ltd.
    MFI: 7g/10mins (190 deg. C, 2.16kg)
    Density: 0.92g/cm3
    Stearic acid Grade: 1801 0.5kg/100.8kg 0.49
    Supplier: Shanghai factory
    Calcium stearate Grade: 1801 0.3kg/100.8kg 0.30
    Supplier: Supplier: Shanghai factory
    total 100.8kg 100%
    • Example 2
  • The components listed below in Table 2 (composition B) were first blended in a high speed mixer in the following order of addition: starch, LDPE, VLDPE, EAA, Calcium stearate, stearic acid, glycerol, and sorbitol. The resulting physical blend was then melt processed on a vented twin screw extruder having melt profile 140/170/175/175/165/155 deg.C, torque < 80%, screw speed 320-350 rpm, vacuum of -0.05 bar and output of 200 kg/h to provide for Blend B. Film was then blown using Blend B. The resulting film had a tensile strength at break of greater than 10 MPa, and an elongation of > 250% as tested using a universal tensile testing machine. The film exhibited excellent antiblock and anti-static properties. Table 2: Composition B
    Component Grade and Supplier Amount %
    Cornstarch Grade: Eatable or industry first class products 42kg/100.8kg 41.66
    Supplier: Shandong Zhucheng Starch Pty Ltd.
    Degree of Substitution: >0.1
    Glycerol Grade: saponification Glycerol or vegetal 11kg/100.8kg 10.91
    Glycerol
    Supplier: Nanjing Soap factory
    Purity: ≥96%
    Boiling Point: >250 deg. C
    Sorbitol Grade: industry Sorbitol 10kg/100.8kg 9.92
    Supplier: Jiangsu Luo'er Gaici Pty Ltd.
    Purity: ≥70%
    Boiling Point: ≈100 deg.C
    EAA Grade: Primacor 3340 12kg/100.8kg 11.91
    Supplier: DOW
    MFI: 10.5 g/10mins (190 deg. C/2.16kg)
    Density: 0.938g/cm3
    ethylene-acrylic acid copolymer having an
    acrylic acid content of 9.5%
    VLDPE Grade: Attane 4404 10kg/100.8kg 9.92
    Supplier: DOW
    MFI: 4g/10mins (190 deg. C, 2.16kg)
    Density: 0.904 g/cm3
    LDPE Grade: 1FTB 15kg/100.8kg 14.89
    Supplier: Beijing Yanshan Pty Ltd.
    MFI: 7g/10mins (190 deg. C, 2.16kg)
    Density: 0.92g/cm3
    Stearic acid Grade: 1801 0.5kg/100.8kg 0.49
    Supplier: Shanghai factory
    Calcium stearate Grade: 1801 0.3kg/100.8kg 0.30
    Supplier: Supplier: Shanghai factory
    total 100.8 kg 100%
    • Example 3
  • The components listed below in Table 3 (composition C) were first blended in a high speed mixer in the following order of addition: starch, EAA, VLDPE, EVA LDPE, Calcium stearate, stearic acid, glycerol, and sorbitol. The resulting physical blend was then melt processed on a vented twin screw extruder having melt profile 140/165/170/170/170/155 deg.C, torque < 80%, screw speed 320-350 rpm, vacuum of -0.05 bar and output of 200 kg/h to provide for Blend C. Blend C was formed into a foam buy melt processing it with a conventional blowing agent masterbatch. The resulting foam is suitable as a soft foam packaging material and has excellent softness and soft touch properties. Table 3: Composition C
    Ingredient Grade and Supplier Amount %
    Cornstarch Grade: Eatable or industry first class products 50kg/105.8kg 47.23
    Supplier: Shandong Zhucheng Starch Pty Ltd.
    Degree of Substitution: >0.1
    Glycerol Grade: saponification Glycerol or vegetal Glycerol 11kg/105.8kg 10.42
    Supplier: Nanjing Soap factory
    Purity: ≥96%
    Boiling Point: >250 deg. C
    Sorbitol Grade: industry Sorbitol 5kg/105.8kg 4.72
    Supplier: Jiangsu Luo'er Gaici Pty Ltd.
    Purity: ≥70%
    Boiling Point: ≈100 deg.C
    EAA Grade: Primacor 3340 12kg/105.8kg 11.34
    Supplier: DOW
    MFI: 10.5 g/10mins (190 deg. C/2.16kg)
    Density: 0.938g/cm3
    ethylene-acrylic acid copolymer having an
    acrylic acid content of 9.5%
    VLDPE Grade: Attane 4404 10kg/105.8kg 9.45
    Supplier: DOW
    MFI: 4g/10mins (190 deg. C, 2.16kg)
    Density: 0.904 g/cm3
    LDPE Grade: 1FTB 11kg/105.8kg 10.42
    Supplier: Beijing Yanshan Pty Ltd.
    MFI: 7g/10mins (190 deg. C, 2.16kg)
    Density: 0.92g/cm3
    EVA Grade: 14-2, V4110J 6kg/105.8kg 5.67
    Supplier: Beijing Yanshan Pty Ltd., Yangzi Pty Ltd.
    MFI: 2 g/10mins (190 deg. C, 2.16kg)
    Density: 0.93 g/cm3
    Stearic acid Grade: 1801 0.5kg/105.8kg 0.47
    Supplier: Shanghai factory
    Calcium stearate Grade: 1801 0.3kg/105.8kg 0.28
    Supplier: Supplier: Shanghai factory
    total 105.8 100%
    • Example 4
  • Blend B was melt processed with 20 wt. % LDPE (melt index 0.3g/10 mins and density of 0.922 g/cm3) and formed into sheet of 0.380 mm thickness. The resulting sheet was thermoformed into a cuspated sheet.
    • Example 5
  • Blend B was blown into 50 micron film and then converted into shopping bags with a loading carrying capacity of 6 kg. The bags were found to have comparable tear, tensile and elongational properties to bags made from HDPE. The film can be easily printed using conventional processes and without Corona pre-treatment.
    • Example 6
  • Blend B was melt processed with 10 wt. % HDPE and blown into a film suitable for use in shopping bag applications. The resulting film was found to be 100% more stiff than a comparable film made from just Blend B.
  • Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
  • The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Claims (16)

  1. A composition comprising very low density polyethylene having a density of less than 0.905g/cm3, preferably from about 0.85g/cm3 to 0.905g/cm3, ethylene acrylic acid copolymer having a melt index of 190°/2.16 kg ranging from 10 g/10 min to 20 g/10 min, one or more polyethylene polymers having a density of greater than 0.905g/cm3, and thermoplastic starch and/or the constituent components thereof.
  2. The composition according to claim 1 in the form of a melt processed blend.
  3. The composition according to claim 1 or 2, wherein the very low density polyethylene is present in an amount ranging from about 5 wt. % to about 25 wt. %, the ethylene acrylic acid copolymer is present in an amount ranging from about 5 wt. % to about 25 wt. %, and the thermoplastic starch and/or the constituent components thereof is present in an amount ranging from about 50 wt. % to about 80 wt. %.
  4. The composition according to any one of claims 1 to 3 further comprising ethylene vinyl acetate copolymer in an amount ranging from about 1 wt. % to about 10 wt. %.
  5. The composition according to any one of claims 1 to 4 wherein the one or more polyethylene polymers having a density of greater than 0.905 g/cm3 are selected from low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene.
  6. The composition according to anyone of claims 1 to 5 further comprising one or more additives selected from calcium stearate, steric acid, magnesium stearate, sodium stearate, oxidised polyethylene, oleamide, stearamide and erucamide.
  7. A method of preparing a polyolefin and thermoplastic starch blend, the method comprising melt processing a composition comprising very low density polyethylene having a density of less than 0.905g/cm3, preferably from about 0.85 g/cm3 to 0.905 g/cm3, ethylene acrylic acid copolymer having a melt index of 190°/2.16 kg ranging from 10 g/10 min to 20 g/10 min, one or more polyethylene polymers having a density of greater than 0.905g/cm3, and thermoplastic starch and/or the constituent components thereof.
  8. The method according to claim 7, wherein the very low density polyethylene is present in an amount ranging from about 5 wt. % to about 25 wt. %, the ethylene acrylic acid copolymer is present in an amount ranging from about 5 wt. % to about 25 wt. %, and the thermoplastic starch and/or the constituent components thereof is present in an amount ranging from about 50 wt. % to about 80 wt. %.
  9. The method according to claim 7 or 8, wherein the composition to be melt processed further comprises ethylene vinyl acetate copolymer in an amount ranging from about 1 wt. % to about 10 wt. %.
  10. The method according to any one of claims 7 to 9, wherein the one or more polyethylene polymers having a density of greater than 0.905 g/cm3 are selected from low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene.
  11. The method according to any one of claims 7 to 10, wherein the so formed polyolefin and thermoplastic starch melt blend is further melt processed with one or more polyethylene polymers having a density greater than 0.905 g/cm3 and selected from low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene.
  12. The method according to claim 11, wherein the so formed polyolefin and thermoplastic starch melt blend and the one or more polyethylene polymers having a density greater than 0.905 g/cm3 are melt processed together in amounts ranging from about 40 wt. % to about 60 wt. % and about 40 wt. % to about 60 wt. %, respectively.
  13. An article comprising or produced from a composition according to any one of claims 1 to 6.
  14. The article according to claim 13 in the form of an extruded or moulded product.
  15. The article according to claim 13 in the form of a film.
  16. An article produced according to the method of any one of claims 7 to 12.
EP09802282.5A 2008-07-31 2009-07-31 Compositions comprising thermoplastic starch Active EP2307495B1 (en)

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PCT/AU2009/000979 WO2010012041A1 (en) 2008-07-31 2009-07-31 Compositions comprising thermoplastic starch

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Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201213424A (en) 2010-08-13 2012-04-01 Tristano Pty Ltd Polymer foam
CN101935408B (en) * 2010-09-03 2012-04-25 北京新华联生物材料有限公司 Biodegradable thermoplastic starch resin for packing material and preparation method and product thereof
CN102134333B (en) * 2010-12-13 2013-04-17 北京宜科博泰生态科技有限公司 High-strength biodegradable thermoplastic starch resin, and preparation method and use thereof
CN102115549B (en) * 2010-12-13 2012-09-05 北京新华联生物材料有限公司 Biodegradable starch-containing high polymer composition and preparation thereof
CN102174215A (en) * 2011-03-25 2011-09-07 苏州汉丰新材料有限公司 Method for preparing starch-based biodegradable packing container for freezing
WO2013043944A1 (en) 2011-09-23 2013-03-28 Dow Global Technologies Llc Olefin-based polymer compositions and articles prepared therefrom
US9718258B2 (en) 2011-12-20 2017-08-01 Kimberly-Clark Worldwide, Inc. Multi-layered film containing a biopolymer
US9327438B2 (en) 2011-12-20 2016-05-03 Kimberly-Clark Worldwide, Inc. Method for forming a thermoplastic composition that contains a plasticized starch polymer
CN104470986B (en) * 2012-05-31 2017-09-15 沙特基础工业公司 Biaxial stretch-formed product
TWI445755B (en) 2012-06-27 2014-07-21 Ind Tech Res Inst Flame-retardant thermoplastic starch material, bio-composite and manufacturing method thereof
FR2993275B1 (en) * 2012-07-13 2014-08-01 Roquette Freres STARCH-BASED THERMOPLASTIC COMPOSITION COMPRISING A FUNCTIONAL COMPOUND GROWTH COPOLYMER
EP2799232A1 (en) * 2013-04-30 2014-11-05 The Procter & Gamble Company Flexible package
JP6498205B2 (en) 2013-09-10 2019-04-10 アーケマ・インコーポレイテッド Antistatic thermoplastic starch alloy
EP3068824B1 (en) 2013-11-14 2018-07-18 Saudi Basic Industries Corporation Bi-axially stretched article and silage film
CA2945660A1 (en) 2014-05-12 2015-11-19 The Procter & Gamble Company Microtextured films with improved tactile impression and/or reduced noise perception
CN104558756A (en) * 2014-05-29 2015-04-29 陈向文 Lightweight polymer filling composite material
JP2017515709A (en) 2014-06-02 2017-06-15 ザ プロクター アンド ギャンブル カンパニー Multilayered thermoplastic polymer film containing polylactic acid
CN108373561A (en) * 2018-02-05 2018-08-07 江南大学 A kind of transparent multiple-factor degradation modification polyethylene film and preparation method thereof
US20210115200A1 (en) * 2018-04-09 2021-04-22 Nano And Advanced Materials Institute Limited A germ-repellent plastic, a manufacturing method therefor, and a germ-repellent plastic item made therefrom
US11970604B2 (en) * 2018-04-09 2024-04-30 Vincent Medical Manufacturing Co., Ltd. Germ-repellent plastic, a gas pathway of a respiratory device containing, and a manufacturing method therefor
JP7253331B2 (en) * 2018-06-05 2023-04-06 日泉ポリテック株式会社 Molded sheet of thermoplastic starch/olefin resin composition and method for producing same
CN110894313B (en) * 2019-11-08 2021-08-27 江苏中科成长环保科技有限公司 Anti-freezing microwave-resistant starch-based tableware and preparation method thereof
US10882977B1 (en) * 2020-01-30 2021-01-05 Edward Showalter Earth plant compostable biodegradable substrate and method of producing the same
US11149131B2 (en) * 2020-01-30 2021-10-19 Edward Showalter Earth plant compostable biodegradable substrate and method of producing the same
CN111662486A (en) * 2020-07-10 2020-09-15 上海叶心材料科技有限公司 Method for improving tensile strength of bio-based degradable material
WO2022253731A1 (en) 2021-06-02 2022-12-08 Periplast Werkzeugbau Und Kunststoffverarbeitung Gmbh & Co. Kg Thermoplastic material and method for producing a molded body from a thermoplastic material, and molded body
DE102022132743A1 (en) 2022-12-08 2024-06-13 Periplast Werkzeugbau Und Kunststoffverarbeitung Gmbh & Co. Kg Thermoplastic material

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB967334A (en) 1960-04-27
US4337181A (en) * 1980-01-17 1982-06-29 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable starch-based blown films
US4770912A (en) * 1987-07-23 1988-09-13 Union Camp Corporation Polyethylene resin blend
US5047253A (en) * 1987-11-30 1991-09-10 Viskase Corporation Multilayer film tube for cook-in meat adhesion and method of making
JP2773894B2 (en) * 1989-03-31 1998-07-09 積水化学工業株式会社 Resin composition for moisture-permeable film or sheet, moisture-permeable film or sheet, and method for producing the same
US5162392A (en) 1989-05-19 1992-11-10 Agri-Tech Industries, Inc. Injection moldable biodegradable starch polymer composite
US5449708A (en) 1993-06-25 1995-09-12 Schiltz; David C. Biodegradable starch-based polymer compositions
CN1037515C (en) * 1993-08-24 1998-02-25 北京市星辰现代控制工程研究所 Biodegradable composition containing starch and its producing method and its use
CN1058736C (en) 1994-05-27 2000-11-22 北京市星辰现代控制工程研究所 Preparing method for biodegradation compound and its use
US5714547A (en) * 1995-08-04 1998-02-03 Inteplast Corporation Polymer blend composition for forming transparent polyethylene film
ITTO980524A1 (en) 1998-06-17 1999-12-17 Novamont Spa COMPOSITIONS CONTAINING STARCH WITH HIGH RESISTANCE TO AGING.
JP2000095285A (en) 1998-09-15 2000-04-04 Cryovac Inc Packaged product utilizing flavor transfer film, and its manufacture and usage therefor
US6605657B1 (en) 1999-12-27 2003-08-12 Polyvalor Societe En Commandite Polymer compositions containing thermoplastic starch
US6231970B1 (en) 2000-01-11 2001-05-15 E. Khashoggi Industries, Llc Thermoplastic starch compositions incorporating a particulate filler component
JP2001198941A (en) * 2000-01-17 2001-07-24 Yazaki Corp Tracking-resistant injection-molded object
JP2002275301A (en) * 2001-03-21 2002-09-25 Sanwa Kako Co Ltd Manufacturing method of crosslinked polyethylene-open cell foam
US20020168518A1 (en) * 2001-05-10 2002-11-14 The Procter & Gamble Company Fibers comprising starch and polymers
JP4805477B2 (en) * 2001-05-28 2011-11-02 電気化学工業株式会社 Stretch film for hand wrap
CN1363625A (en) * 2001-11-15 2002-08-14 天津丹海股份有限公司 Process for preparing bio-degradable resin
CN1297599C (en) * 2004-04-27 2007-01-31 胡靖� Utterly biodegradable packaging film and mulch film
WO2006116861A1 (en) 2005-04-29 2006-11-09 Corporation De L'ecole Polytechnique De Montreal Thermoplastic starch and synthetic polymer blends and method of making
CN104945683A (en) 2006-04-18 2015-09-30 普朗蒂克科技有限公司 Polymeric films
FR2927088B1 (en) 2008-02-01 2011-02-25 Roquette Freres PLASTICIZED STARCH THERMOPLASTIC COMPOSITIONS AND PROCESS FOR THE PREPARATION OF SUCH COMPOSITIONS.
CN101885869A (en) 2009-05-15 2010-11-17 金伯利-克拉克环球有限公司 Flexible thermoplastic film and product thereof

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WO2010012041A1 (en) 2010-02-04
CA2732599A1 (en) 2010-02-04
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AU2009276300A1 (en) 2010-02-04
IL210944A0 (en) 2011-04-28
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MY178915A (en) 2020-10-22
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US20120022188A1 (en) 2012-01-26
EP2307495A4 (en) 2013-07-17
ZA201102519B (en) 2012-06-27
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JP5492889B2 (en) 2014-05-14
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